CN103764770A

CN103764770A - Colorant-containing particles, colorant-containing particle dispersion, and polymer compound

Info

Publication number: CN103764770A
Application number: CN201280041516.XA
Authority: CN
Inventors: 青岛俊栄; 加藤隆志; 高桥秀知
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2011-08-26
Filing date: 2012-08-20
Publication date: 2014-04-30
Also published as: WO2013031561A1; JP2013043962A; US9145497B2; US20140163148A1

Abstract

These colorant-containing particles comprising at least a colorant and a first polymer represented by the general formula (1) have good dispersion properties and dispersion stability. R1 represents an m+n-valent organic linking group; R2 represents a single bond or a divalent linking group; A1 represents a monovalent organic group including at least one group selected from among an organic dye residue, a heterocyclic residue, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a C4 or higher hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group; m represents 1 to 8, n represents 2 to 9, and m+n satisfies 3 to 10; R3 represents a single bond or a divalent linking group; and P1 represents a polymer backbone including a Si atom. (A1-R2)n-R1-(R3-P1)m (1).

Description

Contain the particle of tinting material, particle dispersion and polymer compound containing tinting material

Technical field

The present invention relates to can be used for the particle that contains tinting material of various application and the dispersion liquid that contains it.The invention still further relates to the polymer compound that can be used for various application, comprise dispersion agent.

Background technology

At active research electrophoretic display device (EPD) medium, this is a class iatron always.For indicating meter, this display format is used charged particle (electrophoresis particle), and to the unit for example electrophoresis particle and dispersion medium being sealed between a pair of substrate, apply electric field so that electrophoresis particle alternately towards with away from watching surface and the back side to move.

Described particle (electrophoresis particle) forms an important factor in this technology, and has developed various technology.For instance, propose the various additives such as such as dispersion agent and can suppress electrophoresis particle gathering.The charge stability (for example patent documentation 1 and 2) that the charge polarity dispersion agent different from the charge polarity of described particle can improve electrophoresis particle has also been proposed.

Patent documentation 1 and 2 has disclosed by making to have the monomer of acidic-group or basic group and the polymkeric substance that silicon-containing monomer copolymerization is manufactured.These open cases have also disclosed described polymkeric substance have been joined in the indicating meter particle dispersion that for example contains silicone oil.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2002-338642 communique

Patent documentation 2: Japanese Patent Laid-Open 2011-27781 communique

Summary of the invention

The problem to be solved in the present invention

But, utilize the polymkeric substance described in patent documentation 1 and 2 cannot obtain sufficient dispersity, and the initial viscosity of dispersion liquid tend to higher.In addition, dispersion stabilization deficiency, and dispersion liquid viscosity significantly increases in time.

The present invention has been proposed to address the above problem.Specifically, a target of the present invention is to provide a kind of particle containing tinting material and has the particle dispersion containing tinting material of good dispersity and dispersion stabilization and can be used as for example contributing to the polymer compound of the dispersion agent that improves described dispersion of particles degree and dispersion stabilization.

The means of dealing with problems

The present inventor conducts in-depth research the reason of the dispersity deficiency of the polymkeric substance of investigating patent documentation 1 and 2, and find that this shortcoming is owing to having at random acidic-group or basic group in described polymkeric substance, thereby weakened the consistency between described polymkeric substance and dispersion medium, but also owing to being scheduled to the space behavior of siliceous Component units, thereby weakened containing the consistency between particle and the described polymkeric substance of tinting material.

After further research, the polymkeric substance that the present inventor finds to have multiple end structures or functional end-group and has a particle adsorptivity when as particle dispersion agent improve aspect the dispersity of dispersed particle and dispersion stabilization very effective.Also find that when described structure or functional group being introduced to polymer ends by means of multi-functional thiol's compound composite structure easily limits less and without the polymkeric substance of steric exclusion.After further studying, based on these discoveries, complete the present invention.

Specifically, above-mentioned target is by realizing by following means.

[1], containing the particle of tinting material, it comprises tinting material and by the first polymkeric substance representing with following formula (1):

(A ¹-R ²) _n-R ¹-(R ³-P ¹) _m (1)，

Wherein R ¹represent the organic linking group of (m+n) valency; R ²represent separately singly-bound or divalent linker; A ¹represent separately to contain at least one the unit price organic group of selecting group from being formed by organic dye residue, heterocycle residue, acidic-group, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, the alkyl with more than 4 carbon atom, alkoxysilane group, epoxy group(ing), isocyanate group and hydroxyl; N A ¹group can be identical or different; N R ²group can be identical or different; M representative digit 1 to 8, n representative digit 2 to 9, wherein m+n meets 3 to 10; R ³represent separately singly-bound or divalent linker; P ¹represent to contain Si bond owner chain, and can comprise multiple Component units; M R ³group can be identical or different; And m P ¹group can be identical or different.

[2] according to the particle containing tinting material [1] described, also comprise second polymkeric substance with charged group.

[3] according to the particle containing tinting material [1] or [2] described, the A in wherein said formula (1) ¹be acidic-group, and the charged group of described the second polymkeric substance is basic group.

[4] according to the particle containing tinting material [1] or [2] described, the A in wherein said formula (1) ¹be basic group, and the charged group of described the second polymkeric substance is acidic-group.

[5] according to [1] to the particle containing tinting material described in any one in [4], it is the Component units of 1,000 to 10,000 silicone macromonomer that wherein said the first polymkeric substance has derived from weight average molecular weight.

[6] according to the particle containing tinting material described in any one in [1] to [5], the P in wherein said formula (1) ¹by the main polymer chain representing with following formula (2):

-(P ²) _x-(P ³) _y-(P ⁴) _z (2)，

Wherein P ²expression is derived from the Component units of silicone macromonomer; P ³represent containing silicone and do not there is can the dissociate Component units of group of ion; P ⁴represent containing silicone and there is can the dissociate Component units of group of ion; X, y and z represent the molar fraction of Component units separately, and x+y+z=100, and wherein y and z can be 0, but are 0 when different.

[7] according to [1] to the particle containing tinting material described in any one in [6], wherein in described formula (2), x is 10 to 30, y to be 10 to 30, and z is 40 to 80.

[8], according to the particle containing tinting material described in any one in [1] to [7], the wherein said particle containing tinting material is electrophoresis particle.

[9], containing a particle dispersion for tinting material, comprise according to particle and dispersion medium containing tinting material described in any one in [1] to [8].

[10] according to the particle dispersion containing tinting material [9] described, wherein said dispersion medium contains at least one that select from silicone oil and paraffinic hydrocarbon.

[11] polymer compound, by representing with following formula (1 '):

(A ¹-R ⁴-S) _n-R ¹-(R ³-p ¹) _m (1′)，

Wherein R ¹represent the organic linking group of (m+n) valency; R ⁴represent separately singly-bound or divalent linker; S represents sulphur atom; A ¹represent separately to contain at least one the unit price organic group of selecting group from being formed by organic dye residue, heterocycle residue, acidic-group, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, the alkyl with more than 4 carbon atom, alkoxysilane group, epoxy group(ing), isocyanate group and hydroxyl; N A ¹group can be identical or different; N R ⁴group can be identical or different; M representative digit 1 to 8, n representative digit 2 to 9, wherein m+n meets 3 to 10; R ³represent separately singly-bound or divalent linker; P ¹represent to contain Si bond owner chain, and can comprise multiple Component units; M R ³group can be identical or different; M P ¹group can be identical or different;

-(P ²) _x-(P ³) _y-(P ⁴) _z (2)，

The effect of invention

The present invention can provide a kind of particle containing tinting material and have the particle dispersion containing tinting material of good dispersity and dispersion stabilization and can be used as for example contributing to the polymer compound of the dispersion agent that improves described dispersion of particles degree and dispersion stabilization.

Embodiment

Below describe the present invention in detail.

1. contain the particle of tinting material

The present invention is about a kind of particle containing tinting material, and the described particle containing tinting material comprises at least one tinting material and by the first polymkeric substance representing with following formula (1).Particle containing tinting material process of the present invention is configured to comprise tinting material and the first polymkeric substance, and optionally comprises other materials (example is the second polymkeric substance as will be described later).The state of the tinting material in described particle and the first polymkeric substance is not particularly limited.Described tinting material can disperse and be blended in described the first polymkeric substance, or the particle surface of described tinting material can be through described first polymer-coated.In addition, described tinting material can be surrounded by other materials (example is the second polymkeric substance as will be described later), and described the first polymkeric substance can be adsorbed onto the surface of these materials.

(1) the first polymkeric substance being represented by formula (1)

By the first polymkeric substance representing with following formula (1), in polymer ends, there is A ¹, be the multiple unit price organic groups that comprise at least one group of selecting from following group specifically: organic dye residue, heterocycle residue, acidic-group, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, the alkyl with more than 4 carbon atom, alkoxysilane group, epoxy group(ing), isocyanate group and hydroxyl.The first polymkeric substance thereby have various features, comprises the high absorption property to solid surface, good micelle formation and high surface.For instance, when as dispersion of particles agent such as such as pigment, described the first polymkeric substance contributes to improve described dispersion of particles degree and dispersion stabilization.Described the first polymkeric substance is effective especially for silicone oil or paraffinic hydrocarbon dispersion medium.

Described the first polymkeric substance can homogeneous and is included in equably in described particle, maybe can localize by being non-uniformly distributed in described particle, described containing in the particle of tinting material as long as described the first polymkeric substance is included in.From the viewpoint of dispersity and dispersion stabilization, preferably, described the first Polymer adsorption is to the outmost surface of the described particle containing tinting material.

(A ¹-R ²) _n-R ¹-(R ³-p ¹) _m (1)

In described formula, R ¹represent the organic linking group of (m+n) valency; R ²represent separately the organic linking group of singly-bound or divalence; A ¹represent separately the unit price organic group that contains at least one group of selecting from following group: organic dye residue, heterocycle residue, acidic-group, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, the alkyl with more than 4 carbon atom, alkoxysilane group, epoxy group(ing), isocyanate group and hydroxyl; A ¹and R ²independently of one another can be identical or different in the situation that thering is subscript n; M representative digit 1 to 8, and n representative digit 2 to 9, wherein m+n meets 3 to 10; R ³represent separately singly-bound or divalent linker; And P ¹represent containing Si bond owner chain, and can comprise multiple Component units, wherein R ³and P ¹independently of one another can be identical or different in the situation that thering is subscript m.

In formula (1), A ¹represent separately the unit price organic group that contains at least one group of selecting from following group: organic dye residue, heterocycle residue, acidic-group, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, the alkyl with more than 4 carbon atom, alkoxysilane group, epoxy group(ing), isocyanate group and hydroxyl.A ¹can be identical or different in the situation that thering is subscript n.

By A ¹the organic group representing preferably has adsorptivity to tinting material, maybe when there is the material that surrounds described tinting material, described material (example is the second polymkeric substance as will be described later) is had to adsorptivity.Note, term " absorbed portion " will be used in reference to part (A tinting material and other materials to adsorptivity in due course ¹self or A ¹in contained functional group).

A ¹can there is single absorbed portion or multiple absorbed portion.When there is multiple absorbed portion, these absorbed portions can be identical or different.

A ¹it is the unit price organic group for example producing by absorbed portion and by organic linking group keyed jointing of 1 to 200 carbon atom, 0 to 20 nitrogen-atoms, 0 to 20 nitrogen-atoms, 0 to 100 Sauerstoffatom, 1 to 400 hydrogen atom and 0 to 40 sulphur atom configuration.When the configurable described unit price organic group of described absorbed portion self, described absorbed portion self can be by A ¹the unit price organic group representing.

By A ¹the example of the organic dye residue representing comprises phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolo-pyrrole, anthracene pyridine, anthanthrone, indanthrone, yellow scholar's ketone (flavanthrone), the auspicious ketone of piperazine (perinone), perylene and thioindigo(id)dyes, wherein phthalocyanine, azo lake, anthraquinone, dioxazine and diketopyrrolo-pyrrole dyestuff residue are preferred, and phthalocyanine, anthraquinone and diketopyrrolo-pyrrole dyestuff residue are particularly preferred.

By A ¹the example of the heterocycle residue representing comprises thiophene, furans, xanthene, pyrroles, pyrroline, tetramethyleneimine, dioxolane, pyrazoles, pyrazoline, pyrazolidine, imidazoles, oxazole, thiazole, oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines, diox, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithian, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succimide, phthalic imidine, naphthalimide, glycolylurea, indoles, quinoline, carbazole, acridine, dihydroketoacridine and anthraquinone residue, wherein pyrroline, tetramethyleneimine, imidazoles, triazole, pyridine, piperidines, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succimide, phthalic imidine, naphthalimide, glycolylurea, carbazole, acridine, dihydroketoacridine and anthraquinone residue are preferred.

Organic dye residue and heterocycle residue can comprise one or more substituting groups separately.Described substituent example comprises the alkyl with 1 to 20 carbon atom, for example methyl and ethyl; There is the aryl of 6 to 16 carbon atoms, for example phenyl and naphthyl; Hydroxyl, amino, carboxyl, sulphonamide, N-sulphonamide; There is the acyloxy of 1 to 6 carbon atom, for example acetoxyl group; There is the alkoxyl group of 1 to 20 carbon atom, for example methoxyl group and oxyethyl group; Halogen atom, for example chlorine and bromine; There is the alkoxy carbonyl of 2 to 7 carbon atoms, for example methoxycarbonyl, ethoxy carbonyl and cyclohexyl oxygen base carbonyl; Cyano group; And carbonic ether, for example the carbonic acid tert-butyl ester.The linking group that these substituting groups can configure via the combination of following structural unit or described structural unit is connected to organic dye residue or heterocycle residue.

[Chemical formula 1]

By A ¹the example of the acidic-group representing comprises carboxylic acid group, sulfonic group, sulfate mono ester group, phosphate, monophosphate ester group and boronate.Carboxylic acid group, sulfonic group, sulfate mono ester group, phosphate and monophosphate ester group are preferred, and carboxylic acid group, sulfonic group and phosphate are particularly preferred.

By A ¹the example of the group with basic nitrogen atom representing comprises amino (NH ₂), through replacement imino-(NHR ⁸,-NR ⁹r ¹⁰, wherein R ⁸, R ⁹and R ¹⁰independently of one another represent have 1 to 20 carbon atom alkyl, there is the aryl of more than 6 carbon atom, or there is the aralkyl of more than 7 carbon atom), by with following formula (a1) represent guanidine radicals and by with following formula (a2) represent amidino groups.

[Chemical formula 2]

In formula (a1), R ¹¹and R ¹²represent to have independently of one another 1 to 20 carbon atom alkyl, there is the aryl of more than 6 carbon atom, or there is the aralkyl of more than 7 carbon atom.

In formula (a2), R ¹³and R ¹⁴represent to have independently of one another 1 to 20 carbon atom alkyl, there is the aryl of more than 6 carbon atom, or there is the aralkyl of more than 7 carbon atom.

Preferred example comprises amino (NH ₂), through replacement imino-(NHR ⁸,-NR ⁹r ¹⁰, wherein R ⁸, R ⁹and R ¹⁰represent to have independently of one another alkyl, the phenyl or benzyl of 1 to 10 carbon atom), the guanidine radicals that represented by formula (a1) (in formula (a1), R ¹¹and R ¹²represent to have independently of one another alkyl, the phenyl or benzyl of 1 to 10 carbon atom) and the amidino groups that represented by formula (a2) (in formula (a2), R ¹³and R ¹⁴represent to have independently of one another alkyl, the phenyl or benzyl of 1 to 10 carbon atom).

Particularly preferred example comprises amino (NH ₂), through replacement imino-(NHR ⁸,-NR ⁹r ¹⁰, wherein R ⁸, R ⁹and R ¹⁰represent to have independently of one another alkyl, the phenyl or benzyl of 1 to 5 carbon atom), the guanidine radicals that represented by formula (a1) (in formula (a1), R ¹¹and R ¹²represent to have independently of one another alkyl, the phenyl or benzyl of 1 to 5 carbon atom) and the amidino groups that represented by formula (a2) (in formula (a2), R ¹³and R ¹⁴represent to have independently of one another alkyl, the phenyl or benzyl of 1 to 5 carbon atom).

By A ¹comprise-the NR of example of the urea groups representing ¹⁵cONR ¹⁶r ¹⁷(wherein R ¹⁵, R ¹⁶and R ¹⁷represent independently of one another hydrogen atom, have 1 to 20 carbon atom alkyl, there is the aryl of more than 6 carbon atom, or there is the aralkyl of more than 7 carbon atom), more preferably comprise-NR ¹⁵cONHR ¹⁷(wherein R ¹⁵and R ¹⁷represent independently of one another hydrogen atom, have 1 to 10 carbon atom alkyl, there is the aryl of more than 6 carbon atom, or there is the aralkyl of more than 7 carbon atom), particularly preferably be-NHCONHR ¹⁷(wherein R ¹⁷represent hydrogen atom, have 1 to 10 carbon atom alkyl, there is the aryl of more than 6 carbon atom, or there is the aralkyl of more than 7 carbon atom).

By A ¹comprise-the NHCOOR of example of the carbamate representing ¹⁸,-NR ¹⁹cOOR ²⁰,-OCONHR ²¹,-OCONR ²²r ²³(wherein R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²²and R ²³independently of one another represent have 1 to 20 carbon atom alkyl, there is the aryl of more than 6 carbon atom, or there is the aralkyl of more than 7 carbon atom), more preferably-NHCOOR ¹⁸,-OCONHR ²¹(wherein R ¹⁸and R ²¹independently of one another represent have 1 to 20 carbon atom alkyl, there is the aryl of more than 6 carbon atom, or there is the aralkyl of more than 7 carbon atom), particularly preferably be-NHCOOR ¹⁸,-OCONHR ²¹(wherein R ¹⁸and R ²¹independently of one another represent have 1 to 10 carbon atom alkyl, there is the aryl of more than 6 carbon atom, or there is the aralkyl of more than 7 carbon atom).

By A ¹the example of the group with coordination Sauerstoffatom representing comprises Acetyl Acetone acid esters and crown ether.

By A ¹the example with more than 4 alkyl of carbon atom representing comprises the alkyl with more than 4 carbon atom, there is the aryl of more than 6 carbon atom, and there is the aralkyl of more than 7 carbon atom, more preferably there is the alkyl of 4 to 20 carbon atoms, there is the aryl of 6 to 20 carbon atoms and there is the aralkyl of 7 to 20 carbon atoms, particularly preferably be the alkyl (for example octyl group and dodecyl) with 4 to 15 carbon atoms, there is the aryl (for example phenyl and naphthyl) of 6 to 15 carbon atoms and there is the aralkyl (for example phenmethyl) of 7 to 15 carbon atoms.

By A ¹the example of the alkoxysilane group representing comprises Trimethoxy silane base and triethoxysilicane alkyl.

The preferred embodiment of organic linking group of being combined with absorbed portion comprises singly-bound and by 1 to 100 carbon atom, 0 to 10 nitrogen-atoms, 0 to 50 Sauerstoffatom, 1 to 200 hydrogen atom and 0 to 20 organic linking group that sulphur atom forms.Organic linking group can be unsubstituted, and maybe can have substituting group.

The specific examples of organic linking group comprises following structural unit and the group by the combining and configuring of described structural unit.

[chemical formula 3]

When described organic linking group has substituting group, described substituent example comprises the alkyl with 1 to 20 carbon atom, for example methyl and ethyl; There is the aryl of 6 to 16 carbon atoms, for example phenyl and naphthyl; Hydroxyl, amino, carboxyl, sulphonamide, N-sulphonamide; There is the acyloxy of 1 to 6 carbon atom, for example acetoxyl group; There is the alkoxyl group of 1 to 6 carbon atom, for example methoxyl group and oxyethyl group; Halogen atom, for example chlorine and bromine; There is the alkoxy carbonyl of 2 to 7 carbon atoms, for example methoxycarbonyl, ethoxy carbonyl and cyclohexyl oxygen base carbonyl; Cyano group; And carbonic ether, for example the carbonic acid tert-butyl ester.

Preferably, A ¹contain from organic dye residue, heterocycle residue, acidic-group, the group with basic nitrogen atom, urea groups and there is the unit price organic group of at least one part of selecting the alkyl of more than 4 carbon atom.

More preferably, A ¹by the unit price organic group representing with following formula (3).

[chemical formula 4]

In formula (3), B ¹represent absorbed portion (specifically, the part of selecting from following group: organic dye residue, heterocycle residue, acidic-group, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, the alkyl with more than 4 carbon atom, alkoxysilane group, epoxy group(ing), isocyanate group and hydroxyl), and R ²⁴expression singly-bound or (a+1) the organic linking group of valency.A represents integer 1 to 10, and B ¹can be identical or different in the situation that thering is subscript a.

By B ¹the example of absorbed portion representing and preferred embodiment comprise and A for forming in formula (1) ¹the illustrated identical functional group of absorbed portion.

The part of preferably selecting from following group: organic dye residue, heterocycle residue, acidic-group, the group with basic nitrogen atom, urea groups and there is the alkyl of more than 4 carbon atom.

R ²⁴expression singly-bound or (a+1) the organic linking group of valency, wherein a representative digit 1 to 10.Preferably, a is 1 to 7, is more preferably 1 to 5, particularly preferably 1 to 3.

(a+1) example of the organic linking group of valency comprises by 1 to 100 carbon atom, 0 to 10 nitrogen-atoms, 0 to 50 Sauerstoffatom, 1 to 200 hydrogen atom and 0 to 20 group that sulphur atom forms.(a+1) the organic linking group of valency can be unsubstituted, and maybe can have substituting group.

(a+1) specific examples of the organic linking group of valency comprises following structural unit and the group (can form ring structure) by the combining and configuring of described structural unit.

[chemical formula 5]

R ²⁴be preferably singly-bound or by 1 to 50 carbon atom, 0 to 8 nitrogen-atoms, 0 to 25 Sauerstoffatom, 1 to 100 hydrogen atom and 0 to 10 organic linking group of (a+1) valency that sulphur atom forms, more preferably singly-bound or by 1 to 30 carbon atom, 0 to 6 nitrogen-atoms, 0 to 15 Sauerstoffatom, 1 to 50 hydrogen atom and 0 to 7 organic group that connects of (a+1) valency that sulphur atom forms, be particularly preferably singly-bound or by 1 to 10 carbon atom, 0 to 5 nitrogen-atoms, 0 to 10 Sauerstoffatom, 1 to 30 hydrogen atom and 0 to 5 organic group that connects of (a+1) valency that sulphur atom forms.

When the organic linking group of (a+1) valency has substituting group, described substituent example comprises the alkyl with 1 to 20 carbon atom, for example methyl and ethyl; There is the aryl of 6 to 16 carbon atoms, for example phenyl and naphthyl; Hydroxyl, amino, carboxyl, sulphonamide, N-sulphonamide; There is the acyloxy of 1 to 6 carbon atom, for example acetoxyl group; There is the alkoxyl group of 1 to 6 carbon atom, for example methoxyl group and oxyethyl group; Halogen atom, for example chlorine and bromine; There is the alkoxy carbonyl of 2 to 7 carbon atoms, for example methoxycarbonyl, ethoxy carbonyl and cyclohexyl oxygen base carbonyl; Cyano group; And carbonic ether, for example the carbonic acid tert-butyl ester.

Particularly preferably be the A in the first polymkeric substance being represented by formula (1) ¹the charged group that is acidic-group and the second polymkeric substance (being described subsequently) is basic group, or the A in the first polymkeric substance being represented by formula (1) ¹the charged group that is basic group and the second polymkeric substance (being described subsequently) is acidic-group.

In formula (1), R ²represent separately the organic linking group of singly-bound or divalence.R ²can be identical or different in the situation that thering is subscript n.

The example of the organic linking group of divalence comprises by 1 to 100 carbon atom, 0 to 10 nitrogen-atoms, 0 to 50 Sauerstoffatom, 1 to 200 hydrogen atom and 0 to 20 group that sulphur atom forms.The organic linking group of described divalence can be unsubstituted, and maybe can have substituting group.

The specific examples of the organic linking group of described divalence comprises the structural unit of selecting from the following structural unit G of group and the group by the combining and configuring of described structural unit.

[chemical formula 6]

The G of structural unit group

Preferably, R ²for singly-bound or by 1 to 50 carbon atom, 0 to 8 nitrogen-atoms, 0 to 25 Sauerstoffatom, 1 to 100 hydrogen atom and 0 to 10 organic linking group of the divalence that sulphur atom forms, be more preferably singly-bound or by 1 to 30 carbon atom, 0 to 6 nitrogen-atoms, 0 to 15 Sauerstoffatom, 1 to 50 hydrogen atom and 0 to 7 organic linking group of the divalence that sulphur atom forms, particularly preferably singly-bound or by 1 to 10 carbon atom, 0 to 5 nitrogen-atoms, 0 to 10 Sauerstoffatom, 1 to 30 hydrogen atom and 0 to 5 organic linking group of the divalence that sulphur atom forms.

Specifically, by the polymer compound representing with following formula (1 '), represented the preferred embodiment of the first polymkeric substance being represented by formula (1).

(A ¹-R ⁴-S) _n-R ¹-(R ³-p ¹) _m (1′)

In described formula, A ¹, R ¹, R3, P ¹and n and m have and definition and preferable range identical described in formula (1) separately.S represents sulphur atom, and R ⁴represent singly-bound or the organic linking group of divalence.R ⁴can be identical or different in the situation that thering is subscript n.By R ⁴the example of the organic linking group of divalence representing and preferred form comprise and R in formula (1) ²the organic linking group of illustrated identical divalence and form.

Preferably, R ⁴it is the organic linking group of singly-bound or divalence, the organic linking group of described divalence is to form by the combining and configuring of the structural unit of selecting from the above structural unit G of group or described structural unit and by " 1 to 10 carbon atom, 0 to 5 nitrogen-atoms, 0 to 10 Sauerstoffatom, 1 to 30 hydrogen atom and 0 to 5 sulphur atom ", the organic linking group of wherein said divalence can have substituting group, and described substituent example comprises the alkyl with 1 to 20 carbon atom, for example methyl and ethyl; There is the aryl of 6 to 16 carbon atoms, for example phenyl and naphthyl; Hydroxyl, amino, carboxyl, sulphonamide, N-sulphonamide; There is the acyloxy of 1 to 6 carbon atom, for example acetoxyl group; There is the alkoxyl group of 1 to 6 carbon atom, for example methoxyl group and oxyethyl group; Halogen atom, for example chlorine and bromine; There is the alkoxy carbonyl of 2 to 7 carbon atoms, for example methoxycarbonyl, ethoxy carbonyl and cyclohexyl oxygen base carbonyl; Cyano group; And carbonic ether, for example the carbonic acid tert-butyl ester.

In formula (1) and formula (1 '), R ¹represent the organic linking group of (m+n) valency.M+n meets 3 to 10.

By R ¹the example of the organic linking group of (m+n) valency representing comprises by 1 to 100 carbon atom, 0 to 10 nitrogen-atoms, 0 to 50 Sauerstoffatom, 1 to 200 hydrogen atom and 0 to 20 group that sulphur atom forms.(m+n) the organic linking group of valency can be unsubstituted, and maybe can have substituting group.

(m+n) specific examples of the organic linking group of valency comprises following structural unit and the group (can form ring structure) by the combining and configuring of described structural unit.

[chemical formula 7]

Preferably, (m+n) the organic linking group of valency is by 1 to 60 carbon atom, 0 to 10 nitrogen-atoms, 0 to 40 Sauerstoffatom, 1 to 120 hydrogen atom and 0 to 10 group that sulphur atom forms, being more preferably by 1 to 50 carbon atom, 0 to 10 nitrogen-atoms, 0 to 30 Sauerstoffatom, 1 to 100 hydrogen atom and 0 to 7 group that sulphur atom forms, is particularly preferably by 1 to 40 carbon atom, 0 to 8 nitrogen-atoms, 0 to 20 Sauerstoffatom, 1 to 80 hydrogen atom and 0 to 5 group that sulphur atom forms.

When the organic linking group of (m+n) valency has substituting group, described substituent example comprises the alkyl with 1 to 20 carbon atom, for example methyl and ethyl; There is the aryl of 6 to 16 carbon atoms, for example phenyl and naphthyl; Hydroxyl, amino, carboxyl, sulphonamide, N-sulphonamide; There is the acyloxy of 1 to 6 carbon atom, for example acetoxyl group; There is the alkoxyl group of 1 to 6 carbon atom, for example methoxyl group and oxyethyl group; Halogen atom, for example chlorine and bromine; There is the alkoxy carbonyl of 2 to 7 carbon atoms, for example methoxycarbonyl, ethoxy carbonyl and cyclohexyl oxygen base carbonyl; Cyano group; And carbonic ether, for example the carbonic acid tert-butyl ester.

Below provide by R ¹the specific examples of the organic linking group of (m+n) valency representing arrives (17) as specific examples (1).Should notice that following instance does not limit the present invention.

[chemical formula 8]

[chemical formula 9]

In these particular instances, from the availability of raw material, synthetic easiness and the solvability all kinds of SOLVENTS, below the organic linking group of (m+n) valency be most preferred.

[Chemical formula 1 0]

In formula (1) and formula (1 '), m represents 1 to 8.M is preferably 1 to 5, is more preferably 1 to 4, and particularly preferably 1 to 3.M is preferably 1 to 5, is more preferably 1 to 4, and particularly preferably 1 to 3.

In formula (1) and formula (1 '), n represents 2 to 9.N is preferably 2 to 8, is more preferably 2 to 7, and particularly preferably 3 to 6.

In formula (1) and formula (1 '), R ³represent separately singly-bound or divalent linker, and R ³can be identical or different in the situation that thering is subscript m.By R ³the example of divalent linker representing comprise with for R ²illustrated identical divalent linker.R ³be preferably singly-bound or-S-.

In formula (1) and formula (1 '), P ¹represent containing Si bond owner chain, and can from various main polymer chains, select, as decided according to intended purpose.P ¹can be identical or different in the situation that thering is subscript m.P ¹contain at least one Component units, and can contain more than two Component units.Work as P ¹while containing more than two Component units, at least one in described Component units is the Component units containing Si atom.

P ¹contain at least one Component units containing Si atom.Described Component units is preferably the Component units derived from silicone monomer, and described silicone monomer can be silicone macromonomer.As used herein, " macromonomer (macromer/macromonomer) " is used in reference to the oligomer (polymerization degree is approximately 2 to 300) with polymerizable functional group or the general property term with the polymkeric substance of polymerizable functional group, and described macromonomer has polymkeric substance and monomer character concurrently.Preferably, described Component units is derived from silicone macromonomer and weight average molecular weight be 1,000 to 50,000 Component units of (more preferably 1,000 to 10,000, more preferably 1,000 to 5,000).

Preferably, P ¹have at least one from the polymkeric substance by vinyl monomer or multipolymer, ester polymer, ether polymer, urethane polymer, amide polymer, polymkeric substance based on epoxy group(ing), silicone polymer with and modified product or multipolymer (for example, polyethers/polyurethane ester copolymer and polyethers/vinyl monomer polymers copolymers, described multipolymer can be any in random copolymers, segmented copolymer and graft copolymer) main polymer chain selected in the group that forms.More preferably, P ¹have at least one from the polymkeric substance by vinyl monomer or multipolymer, ester polymer, ether polymer, urethane polymer with and group that modified product or multipolymer were formed the main polymer chain selected.Preferably, P ¹it is the main polymer chain of selecting from the polymkeric substance of vinyl monomer or multipolymer.

Preferably, described polymkeric substance dissolves in organic solvent.For instance, when described polymkeric substance is as dispersion agent and while having lower consistency with organic solvent, may weaken and the consistency of dispersion medium, and possibly cannot obtain the adsorption layer with enough dispersion stabilizations.

P ¹be preferably by the main polymer chain representing with following formula (2).

-(P ²) _x-(P ³) _y-(P ⁴) _z (2)

In described formula, P ²expression is derived from the Component units of silicone macromonomer; P ³represent containing silicone and do not there is can the dissociate Component units of group of ion; P ⁴represent containing silicone and there is can the dissociate Component units of group of ion; X, y and z represent the molar fraction of component separately, and x+y+z=100, and wherein y and z can be 0, but are 0 when different.

Derive P ²the example of silicone macromonomer be included in an end and have the silicone compounds of epoxy group(ing), specifically, comprise the silicone compounds being represented by following structural formula 1.The silicone compounds that has epoxy group(ing) at an end has represented one of these silicone compounds.More particularly, for example, silicone macromonomer can be commercially available prod, for example, can derive from the X-22-173DX (trade(brand)name) of silicone company of SHIN-ETSU HANTOTAI (Shin-Etsu Silicone).

[Chemical formula 1 1]

Structural formula 1

In structural formula 1, R ^{1 '}represent hydrogen atom or have the alkyl of 1 to 4 carbon atom, n represents natural number (for example 1 to 1,000, be desirably 3 to 100), and x represents integer 1 to 3.

Derive P ²the example of silicone macromonomer be included in an end and have the dimethyl-silicon one monomers of (methyl) acrylate group.Specific examples silicone compounds that following structural formula 2 represents of serving as reasons.More particularly, for example, silicone macromonomer can be commercially available prod, for example Silaplane FM-0711, FM-0721 and FM-0725 (trade(brand)name, Chisso Corporation (Chisso)) and X-22-174DX, X-22-2426 and X-22-2475 (trade(brand)name, silicone company of SHIN-ETSU HANTOTAI).

[Chemical formula 1 2]

Structural formula 2

In structural formula 2, R ¹represent hydrogen atom or methyl; R ^{1 '}represent hydrogen atom or there is the alkyl of 1 to 4 carbon atom; N represents natural number (for example 1 to 1,000, be desirably 3 to 100); And x represents integer 1 to 3.

Derive P ²the example of silicone macromonomer comprise by the monomer representing with following formula (I) and formula (II).

[Chemical formula 1 3]

In formula (I) and formula (II), R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁹and R ¹⁰represent independently of one another hydrogen atom, there is the alkyl of 1 to 4 carbon atom or there is the fluoroalkyl of 1 to 4 carbon atom.

R ⁸represent hydrogen atom or methyl.

N, 1 and m represent independently of one another integer 1 to 1,000.

X represents integer 1 to 3.

In formula (I), it is desirable to R ¹and R ⁵represent butyl, R ², R ³, R ⁴, R ⁶and R ⁷represent methyl, R ⁸represent methyl, n and m represent integer 1 to 5 independently of one another, and x represents integer 1 to 3.

In formula (II), it is desirable to R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁹and R ¹⁰represent methyl, R ⁸represent methyl, n, 1 and m represent independently of one another integer 1 to 3, and x represents integer 1 to 3.

The concrete limiting examples of the monomer being represented by formula (I) and formula (II) is below provided.

[Chemical formula 1 4]

Exemplary compound 1 (A Marx (AZmax) company; MCS-M11 (trade(brand)name))

M, n=2 to 4

Molecular weight (molecular weight)=800 to 1,000

Exemplary compound 2 (A Marx (AZmax) company; RTT-1011 (trade(brand)name))

n＝1

Molecular weight (molecular weight)=570 to 620

In the mass ratio with respect to total polymer, form by P ¹the ratio of the silicone chains component in the silicone polymer of main polymer chain representing is desirably 3% to 60%, and more desirably 5% to 40%.

Formation is by P ¹the weight average molecular weight of the silicone polymer of the main polymer chain representing is desirably 500 to 1,000,000, is more desirably 500 to 100,000, is desirably especially 500 to 10,000.

In formula (2), P ³represent containing silicone and do not there is can the dissociate Component units of group of ion.As used herein, term " ion can dissociate group " be used to refer to acidic-group and basic group with and salt.

Derive P ³the example of monomer comprise vinyl monomer.Vinyl monomer is not particularly limited.Preferred embodiment comprises (methyl) acrylate, crotonate, vinyl acetate, maleic acid ester, FUMARIC ACID TECH GRADE diester, methylene-succinic acid diester, (methyl) acrylamide, vinylbenzene, Vinyl Ether, ketene, alkene, maleimide and (methyl) vinyl cyanide.These preferred embodiments of vinyl monomer are below described.

The example of (methyl) acrylate comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) 2-EHA, the tertiary monooctyl ester of (methyl) vinylformic acid, (methyl) dodecylacrylate, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) vinylformic acid 3-phenoxy group-2-hydroxy propyl ester, (methyl) vinylformic acid 2-chloroethene ester, (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl methyl esters, (methyl) vinyl acrylate, (methyl) vinylformic acid 2-phenyl vinyl acetate, (methyl) vinylformic acid 1-propylene, (methyl) allyl acrylate, (methyl) vinylformic acid 2-allyloxy ethyl ester, (methyl) vinylformic acid alkynes propyl ester, (methyl) vinylformic acid benzene methyl, diethylene glycol monomethyl ether (methyl) acrylate, diethylene glycol monoethyl ether (methyl) acrylate, triethylene glycol monomethyl ether (methyl) acrylate, Triethylene glycol ethyl ether (methyl) acrylate, poly glycol monomethyl ether (methyl) acrylate, polyethyleneglycol ether (methyl) acrylate, (methyl) vinylformic acid beta-phenoxy ethoxy ethyl ester, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, (methyl) vinylformic acid two cyclopentenes esters, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid octafluoro pentyl ester, (methyl) vinylformic acid perfluoro capryl ethyl ester, (methyl) vinylformic acid two encircles pentyl ester, (methyl) vinylformic acid tribromo phenylester, (methyl) vinylformic acid tribromophenoxy ethyl ester and gamma-butyrolactone (methyl) acrylate.

Particularly preferably be by the monomer representing with following formula (III).

[Chemical formula 1 5]

[in described formula, R ²represent hydrogen atom or methyl; R ³represent hydrogen atom or there is the alkyl of 1 to 4 carbon atom, being preferably methyl.Preferably, R ²and R ³it is methyl simultaneously.X represents integer 1 to 3, is preferably 2; And y represents to be less than or equal to 25 natural number, be preferably 1 to 20, more preferably 2 to 10.] these monomers are preferred, because they have containing (gathering) the alkane glycol chains that is less than or equals 25 oxyalkylene repeating units, and these monomers are adsorbed onto the particle being insoluble in solvent as the integrant of multipolymer, and utilize by the space behavior of (gathering) alkane glycol chains performance and carry out stable particle dispersion liquid.

The example of crotonate comprises butyl crotonate and the own ester of butenoic acid.

The example of vinyl acetate comprises vinyl-acetic ester, vinyl chloroacetate, propionate, vinyl butyrate, methoxyacetic acid vinyl acetate and vinyl benzoate.

The example of maleic acid ester comprises dimethyl maleate, diethyl maleate and dibutyl maleate.

The example of FUMARIC ACID TECH GRADE diester comprises dimethyl fumarate, diethyl fumarate and dibutyl fumarate.

The example of methylene-succinic acid diester comprises dimethyl itaconate, diethyl itaconate and dibutyl itaconate.

The example of (methyl) acrylamide comprises (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-normal-butyl acryl (methyl) acid amides, the N-tertiary butyl (methyl) acrylamide, N-cyclohexyl (methyl) acrylamide, N-(2-methoxy ethyl) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-phenyl (methyl) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N phenyl acrylamide, N-phenmethyl (methyl) acrylamide, (methyl) acryloyl morpholine, diacetone acrylamide, N hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, vinyl (methyl) acrylamide, N, N-diallyl (methyl) acrylamide and N-allyl group (methyl) acrylamide.

Cinnamic example comprises vinylbenzene, vinyl toluene, dimethyl styrene, Three methyl Benzene ethene, ethyl styrene, isopropyl benzene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chloro-styrene, dichlorostyrene, bromstyrol, 1-chloro-4-methyl-benzene, is subject to hydroxy styrenes, phenylformic acid vinyl methyl esters and the alpha-methyl styrene of group (for example t-Boc) protection of available acidic substance deprotection.

The example of Vinyl Ether comprises ethylene methacrylic ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl Vinyl Ether, propyl vinyl ether, butyl vinyl ether, hexyl Vinyl Ether, octyl group Vinyl Ether, methoxy ethyl Vinyl Ether and phenylvinyl ether.

The example of ketene comprises ethylene methacrylic ketone, ethyl ketene, propyl ethylene ketone and phenyl ketene.

The example of alkene comprises ethene, propylene, iso-butylene, divinyl and isoprene.

The example of maleimide comprises maleimide, butyl maleimide, cyclohexyl maleimide and phenyl maleimide.

Also likely use (methyl) vinyl cyanide, heterocyclic radical (for example vinyl pyridine, NVP and vinylcarbazole), N-vinyl formamide, N-vinyl acetamide, N-vinyl imidazole and vinyl caprolactone through vinyl substituted.

Except these compounds, also likely use and for example have as the vinyl monomer of the functional groups such as carbamate groups, urea groups, sulfoamido, phenolic group and imide.These monomers with carbamate groups or urea groups can suitably synthesize by using the addition reaction of for example isocyanate group and hydroxyl or nitrogen base, specifically, described addition reaction is for example contain the monomer of isocyanate group and have the compound of single hydroxyl or the addition reaction with the compound that contains single primary amino or secondary amino group, or hydroxyl or the monomer of primary amino or secondary amino group and the addition reaction of monoisocyanates.

In formula (2), P ⁴represent containing silicone and there is can the dissociate Component units of group of ion.

Derive P ⁴the example of monomer comprise vinyl monomer.Vinyl monomer is preferably has acidic-group or its salt as can the dissociate vinyl monomer of group of described ion.The preferred embodiment of these vinyl monomers is below described.

The example with the vinyl monomer of acidic-group comprises and has the vinyl monomer of carboxyl and have a sulfonic vinyl monomer.

The example with the vinyl monomer of carboxyl comprises (methyl) vinylformic acid, vinyl benzoic acid, maleic acid, maleic acid mono alkyl ester, FUMARIC ACID TECH GRADE, methylene-succinic acid, butenoic acid, styracin and acrylic acid dimer.As another example, for example can also use the product of the addition reaction of the cyclic anhydrides such as the hydroxyl monomers such as (methyl) vinylformic acid 2-hydroxy methacrylate and MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride and such as cyclohexane cyclohexanedimethanodibasic acid anhydride.Also likely use for example ω-carboxyl-polycaprolactone list (methyl) acrylate.Can use such as MALEIC ANHYDRIDE, itaconic anhydride and methyl-maleic acid acid anhydride etc. to contain the precursor of anhydride monomers as carboxyl.In these examples, from the viewpoint of the factors such as such as copolymerization easiness, cost and solvability, (methyl) vinylformic acid is particularly preferred.

Example containing sulfonic vinyl monomer comprises 2-acrylamide-2-methyl propane sulfonic.The example with the vinyl monomer of phosphate comprises mono phosphoric acid ester (2-acryloxy ethyl ester) and mono phosphoric acid ester (1-methyl-2-acryloxy ethyl ester).

For instance, the vinyl monomer of phenolic hydroxy group and the vinyl monomer containing sulphonamide also can be as the vinyl monomers with acidic-group.

In formula (2), x, y and z represent the molar fraction of component separately, and x+y+z=100, and wherein y and z can be 0, but are 0 when different.X is preferably greater than 0 and be less than or equal to 30, y and be preferably 0 to 30, and z is preferably 0 to 80.Particularly preferably, x is 10 to 30, y to be 10 to 30, and z is 40 to 80.

For instance, the weight average molecular weight of the first polymkeric substance is desirably 10,000 to 1,000,000, is more desirably 50,000 to 300,000.

The preferred embodiment of the first polymkeric substance comprises by the polymer compound representing with following formula (4).

(A ¹-R ⁴-S) _n-R ¹-(S-P ¹) _m (4)

In formula (4), A ¹, R ¹, P ¹and the definition of m and n is identical with formula (1) with preferable range.R ⁴represent singly-bound or the organic linking group of divalence.R ⁴can be identical or different in the situation that thering is subscript n.By R ⁴the example of the organic linking group of divalence representing and preferred form comprise and R in formula (1) ²the organic linking group of illustrated identical divalence and form.Formula (4) compound can be by being used (A ¹-R ⁴-S) _n-R ¹-(SH) _mas chain-transfer agent, make two or more formation P ¹monomer copolymerization and easily manufacture.To describe after a while synthetic method in detail.

The polymer compound being represented by formula (4) is preferably R ¹, R ⁴, P ¹, the compound that meets the following conditions of m and n.

R ¹: specific examples (1), (2), (10), (11), (16) or (17)

R ⁴: (the organic linking group of described divalence can have substituting group for singly-bound or the organic linking group of divalence that forms by the combining and configuring of the structural unit of selecting from the said structure unit G of group or described structural unit and by " 1 to 10 carbon atom, 0 to 5 nitrogen-atoms, 0 to 10 Sauerstoffatom, 1 to 30 hydrogen atom and 0 to 5 sulphur atom ", and described substituent example comprises the alkyl with 1 to 20 carbon atom, for example methyl and ethyl; There is the aryl of 6 to 16 carbon atoms, for example phenyl and naphthyl; Hydroxyl, amino, carboxyl, sulphonamide, N-sulphonamide; There is the acyloxy of 1 to 6 carbon atom, for example acetoxyl group; There is the alkoxyl group of 1 to 6 carbon atom, for example methoxyl group and oxyethyl group; Halogen atom, for example chlorine and bromine; There is the alkoxy carbonyl of 2 to 7 carbon atoms, for example methoxycarbonyl, ethoxy carbonyl and cyclohexyl oxygen base carbonyl; Cyano group; And carbonic ether, for example the carbonic acid tert-butyl ester.)。

P ¹：-(P ²) _x-(P ³) _y-(P ⁴) _z (2)

In formula (2), P ²expression is derived from the Component units of silicone macromonomer; P ³represent containing silicone and do not there is ion can dissociate group and the Component units derived from (methyl) acrylate, crotonate, vinyl acetate, maleic acid ester, FUMARIC ACID TECH GRADE diester, methylene-succinic acid diester, (methyl) acrylamide, vinylbenzene, Vinyl Ether, ketene, alkene, maleimide and (methyl) vinyl cyanide; P ⁴represent containing silicone and do not there is can dissociate group and derived from carboxylic vinyl monomer or containing the Component units of sulfonic vinyl monomer of ion; X, y and z represent the mol ratio of component separately, and x+y+z=100, and wherein x is greater than 0 and to be less than or equal to 30, y be 0 to 30, and z is 0 to 80.

M:1 to 3

N:3 to 6

The acid number of the first polymkeric substance is not particularly limited.When serving as dispersion agent, the acid number of described the first polymkeric substance is preferably less than or equal to 300 (milligram KOH/ gram), is more preferably less than or equals 250 (milligram KOH/ gram), is particularly preferably less than or equal to 200 (milligram KOH/ gram).Acid esters may damage dispersion of particles degree and dispersion stabilization containing tinting material higher than 200 (milligram KOH/ gram).

The molecular weight of described the first polymkeric substance is preferably 3,000 to 80,000 with regard to weight average molecular weight, and more preferably 5,000 to 50,000, be particularly preferably 7,000 to 30,000.In the case of being limited in the weight average molecular weight within the scope of these, the absorbed portion that is incorporated into polymer ends can fully represent effect, and described polymkeric substance can represent premium properties, comprises and is adsorbed onto solid surface, micelle formation and surfactivity.Exactly, when described the first polymkeric substance serves as dispersion agent, the dispersity that can realize ideal and dispersion stabilization.

(synthetic method)

The synthetic method of the first polymkeric substance being represented by formula (1) is not particularly limited, and described the first polymkeric substance can be by synthesizing with following methods.

First method:

Polyreaction, the polymkeric substance that wherein makes to have the introducing functional end-group of selecting from for example carboxyl, hydroxyl and amino with have more than one absorbed portion sour halogenide, there is the alkyl halide of more than one absorbed portion or there is the isocyanate reaction of more than one absorbed portion.

Second method:

Michael reaction (Michael addition reaction), wherein makes to have the polymkeric substance of introducing end carbon-to-carbon double bond and the thiol reactant with more than one absorbed portion.

The third method:

In the situation that there is free-radical generating agent, make to have the polymkeric substance of introducing end carbon-to-carbon double bond and the thiol reactant with absorbed portion.

The 4th kind of method:

In the situation that there is free-radical generating agent, make the polymkeric substance with introducing end mercaptan react with the compound with carbon-to-carbon double bond and absorbed portion.

Lung biopsy:

Radical polymerization, makes reactive vinyl monomer the mercaptan compound that wherein has more than one absorbed portion in existence.

For ease of synthetic, preferably, by using described the second synthetic method, the 3rd synthetic method, the 4th synthetic method and the 5th synthetic method, more preferably by described the 3rd synthetic method, the 4th synthetic method and the 5th synthetic method, synthesize polymer compound of the present invention.When polymer compound of the present invention has the structure being represented by formula (4), most preferably use described the 5th synthetic method to synthesize being convenient to.

More particularly, by carrying out described the 5th synthetic method in the case of existing by the radical polymerization the compound representing with following formula (5) is incompatible.

(A ¹-R ⁴-S) _n-R ¹-(SH) _m (5)

Symbol in formula (5) has and definition and preferable range identical in formula (1).SH means thiol group.

The compound being represented by formula (5) can be used for example following the 6th kind of method and the 7th kind of method to synthesize.For ease of synthetic, more preferably the 7th kind of method.

The 6th kind of method:

The halide compound with more than one absorbed portion is changed into mercaptan compound (for example, by reacting and be hydrolyzed with thiocarbamide; Directly react with NaSH; And by with CH ₃cOSNa reaction is hydrolyzed).

The 7th kind of method:

Addition reaction, wherein makes per molecule have the compound of 3 to 10 sulfydryls and the compound reaction of the functional group that has absorbed portion and can react with sulfydryl.

The preferred embodiment of the functional group that can react with sulfydryl using in the 7th kind of method comprises sour halogenide, alkyl halide, isocyanic ester and carbon-to-carbon double bond.Particularly preferably, the functional group that can react with sulfydryl is carbon-to-carbon double bond, and described addition reaction is Radical Addition.For with the reactivity of sulfydryl for, carbon-to-carbon double bond is preferably through monosubstituted or through disubstituted vinyl.

The concrete limiting examples [concrete example (18) is to specific examples (34)] that below provides per molecule to there is the compound of 3 to 10 sulfydryls.

[Chemical formula 1 6]

From the viewpoint of raw material utilizability, synthetic easiness and the solubleness all kinds of SOLVENTS, below compound be particularly preferred.

[Chemical formula 1 7]

The compound (having specifically, the compound of carbon-to-carbon double bond and at least one part of selecting from organic dye residue, heterocycle residue, acidic-group, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, the alkyl with more than 4 carbon atom, alkoxysilane group, epoxy group(ing), isocyanate group and hydroxyl) with absorbed portion and carbon-to-carbon double bond is not particularly limited.Example comprises following.

[Chemical formula 1 8]

[Chemical formula 1 9]

[Chemical formula 2 0]

[Chemical formula 2 1]

[Chemical formula 2 2]

[Chemical formula 2 3]

The compound that per molecule has 3 to 10 sulfydryls can be by being used for example following methods (mercaptan-alkene reaction method) to obtain with the Radical Addition product of the compound with absorbed portion and carbon-to-carbon double bond: the compound wherein per molecule to 3 to 10 sulfydryls, and reacts to 100 ℃ at approximately 50 ℃ with the compound dissolution with absorbed portion and carbon-to-carbon double bond in suitable solvent in the situation that adding free-radical generating agent.

For the solvent of mercaptan-alkene reaction method, can be to there is according to per molecule any suitable solvent that the solubleness of the compound of 3 to 10 sulfydryls, the compound with absorbed portion and carbon-to-carbon double bond and Radical Addition product is selected.

The example of described solvent comprises methyl alcohol, ethanol, propyl alcohol, Virahol, 1-methoxy-2-propanol, acetic acid 1-methoxyl group-2-propyl ester, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetic acid methoxyl group propyl ester, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dimethyl formamide, trichloromethane and toluene.The mixture that these solvents can be used as two or more solvents is used.

The example of free-radical generating agent comprises azo-compound, and for example 2,2 '-azo two (isopropyl cyanides) is (AIBN), 2,2 '-azo is two-(2,4 '-methyl pentane nitrile) and the two isopropylformic acid dimethyl esters of 2,2 '-azo; Superoxide, for example Benzoyl Peroxide; And persulphate, for example Potassium Persulphate and ammonium persulphate.

The monomer using in the 5th kind of synthetic method has formed the main polymer chain being represented by formula (1) after polyreaction.Therefore, described monomer can be from for example silicone macromonomer and have at least one that select the vinyl monomer of (methyl) acrylate and carboxyl.Vinyl monomer can, separately for polyreaction, maybe can make two or more vinyl monomer copolymerization.

Described the first polymkeric substance is preferably the polymkeric substance by using known usual way that vinyl monomer and formula (5) compound polymerization are obtained.Formula of the present invention (5) compound serves as chain-transfer agent, and can be referred to as " chain-transfer agent ".

For instance, vinyl monomer and chain-transfer agent are dissolved in suitable solvent, and approximately 50 ℃ to 220 ℃ at the polymerization (solution polymerization process) by adding radical polymerization initiator.

The solvent using in solution polymerization process can be any suitable solvent of selecting according to the solubleness of monomer used and product multipolymer.Example comprises methyl alcohol, ethanol, propyl alcohol, Virahol, 1-methoxy-2-propanol, acetic acid 1-methoxyl group-2-propyl ester, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetic acid methoxyl group propyl ester, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dimethyl formamide, trichloromethane and toluene.The mixture that these solvents can be used as two or more solvents is used.

The example of radical polymerization initiator comprises azo-compound, and for example 2,2 '-azo two (isopropyl cyanides) is (AIBN), 2,2 '-azo is two-(2,4 '-methyl pentane nitrile) and the two isopropylformic acid dimethyl esters of 2,2 '-azo; Superoxide, for example Benzoyl Peroxide; And persulphate, for example Potassium Persulphate and ammonium persulphate.

The first polymer phase is not particularly limited for the ratio of tinting material.From improving the viewpoint of dispersity and dispersion stabilization, the first polymer content is preferably 1 quality % to 60 quality %, and more preferably 3 quality % are to 50 quality %, and more preferably 5 quality % are to 40 quality %.

When the first polymkeric substance is used to join dispersion agent form in dispersion medium, for described dispersion medium, it, to 5 quality %, is more desirably that 0.01 quality % is to 3 quality % that described the first polymkeric substance is desirably for example 0.0001 quality %.

(2) tinting material

Of the present inventionly containing contained tinting material in the particle of tinting material, be not particularly limited, and can be for example organic or inorganic pigment or oily soluble dye.Described tinting material can be any known tinting material, for example magnetic powder (for example magnetite and wustite), carbon black, titanium oxide, magnesium oxide, zinc oxide, CuPc green pigment (phthalocyanine copper cyan color), azophosphine pigment, azo violet red pigment, quinoline Azone red-purple pigment, red pigment, veridian and blue pigments.The concrete representative example of tinting material comprises aniline blue, Ka Keyi indigo plant (carcoyl blue), chrome yellow, dark blue, Du Pont's oil red (Du Pont oil red), quinoline yellow, protochloride methyl indigo plant, phthalocyanine blue, oxalic acid Victoria Green WPB, lamp carbon black, rose bengal (rose bengal), C.I. pigment red 48: 1, C.I. pigment red 122, C.I. Pigment red 57: 1, C.I. Pigment Yellow 73 97, C.I. pigment Blue 15: 1 and C.I. pigment Blue 15: 3.

The colorant content containing in the particle of tinting material of the present invention is not particularly limited, and can determine preferable range according to intended purpose.For instance, when containing in addition second polymkeric substance (being described in hereinafter) with charged group, for the second polymkeric substance, colorant content is desirably 10 quality % to 99 quality %, is more desirably that 30 quality % are to 99 quality %.

(3) there is the second polymkeric substance of charged group

Particle containing tinting material of the present invention can contain second polymkeric substance with charged group in addition.The particle containing tinting material that contains second polymkeric substance with charged group has become electrophoresis particle, and can be as for example for example, electrophoresis particle for display application (Electronic Paper).Preferably, second polymkeric substance with charged group exists round toner, but the form of the second polymkeric substance is not limited to this.

Described the second polymkeric substance preferably has alkalescence or acidic-group as functional group.Described functional group can be the group that serves as charged group, can be maybe and the described independently group of group that serves as charged group.Preferably, described functional group is the group that serves as charged group.As used herein, " charged group " comprises anionic and cationic ionic group and high polar group.The latter's example comprises fluorine-based.

After polymerization, can there is band electric process.For instance, the group of positively charged (being described after a while) can be making separately containing the monomer polymerization of tertiary amine or make described monomer with other monomer copolymerizations and the group of acquisition after tertiary amine is changed into quaternary amine.Electronegative group can be making separately carboxylic monomer polymerization or make described monomer and other monomer copolymerizations and for example, form the group of acquisition after salt by adding alkali (amine) with carboxyl.Band electric process can be for example carrying out after mixed colorant.

The charged group of described the second polymkeric substance is preferably alkali (" cationic group " hereinafter) or acid (" anionic group " hereinafter).The example of described cationic group comprises amino and quaternary ammonium group (comprising its salt).For instance, cationic group is given particle containing tinting material with straight polarity.The example of anionic group comprises phenolic group, carboxyl, formic acid ester group, sulfonic group, sulfonate group, phosphate, phosphate-based and tetraphenylboron base (comprising its salt).For instance, anionic group is given particle containing tinting material with negative polarity.

The homopolymer that the example of described the second polymkeric substance comprises the monomer with charged group and there is the monomer of charged group and the multipolymer of other monomers (not thering is the monomer of charged group).Herein and hereinafter, " (methyl) acrylate " comprises " acrylate " and " methacrylic ester ".

The example with the monomer of charged group comprises the monomer (" anionic monomer " hereinafter) that has the monomer (" cationic monomer " hereinafter) of cationic group and have anionic group.

The example of cationic monomer comprises (methyl) acrylate with aliphatics amino, for example (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-diethylamino ethyl ester, (methyl) vinylformic acid N, N-dibutylamino ethyl ester, (methyl) vinylformic acid N, N-hydroxyethylamino ethyl ester, (methyl) vinylformic acid N-ethylamino ethyl ester, (methyl) vinylformic acid N-octyl group-N-ethylamino ethyl ester and (methyl) vinylformic acid N, N-dihexyl amino ethyl ester; The aromatic series with nitrogen-containing group is substituted vinyl monomer, for example dimethylamino vinylbenzene, diethylamino vinylbenzene, dimethylaminomethyl vinylbenzene and dioctyl amino-benzene ethene; Nitrogenous vinyl ether monomers, for example vinyl-N-ethyl-N-phenyl amino ether, vinyl-N-butyl-N-phenyl amino ether, trolamine divinyl ether, vinyl diphenyl amino ether, N-vinyl hydroxyethylbenzene methane amide and m-aminophenyl base Vinyl Ether; Pyrroles, for example vinyl-amine and N-vinyl pyrrole; Pyrroline, for example N-vinyl-2-pyrroline and N-vinyl-3-pyrroline; Tetramethyleneimine, for example N-ethenyl pyrrolidone, ethenyl pyrrolidone amino ethers and NVP; Imidazoles, for example N-vinyl-glyoxal ethyline; Tetrahydroglyoxaline, for example N-Vinylimdozoline; Indoles, for example N-vinyl indoles; Indoline, for example N-vinyl indoline; Carbazole, for example N-vinylcarbazole, 3, the bromo-N-vinylcarbazole of 6-bis-; Pyridine, for example 2-vinyl pyridine, 4-vinylpridine and 2-methyl-5-vinylpyrine; Piperidines, for example (methyl) acryl piperidines, N-vinyl piperidone and N-vinyl piperazine; Quinoline, for example 2-vinylquinoline and 4-vinylquinoline; Pyrazoles, for example N-vinyl pyrazoles and N-vinyl pyrazoles quinoline; Oxazole, for example 2-Yi Xi Ji oxazole; Yi for example, Ji oxazine, 4-Yi Xi Ji oxazine and (methyl) vinylformic acid morpholinyl ethyl ester.From the viewpoint of versatility, as cationic monomer, particularly preferably be (methyl) acrylate with aliphatics amino, for example (methyl) vinylformic acid N, N-dimethylamino ethyl ester and (methyl) vinylformic acid N, N-diethylamino ethyl ester.Preferably, these (methyl) acrylate are form uses of the committee's ammonium salt to be produced before and after polymerization.Committee's ammonium salt can be by for example making described compound react to obtain with alkyl halide or tosylate.

The example of anionic monomer is as follows.Carboxylic acid monomer's specific examples comprises (methyl) vinylformic acid, butenoic acid, methylene-succinic acid, maleic acid, FUMARIC ACID TECH GRADE, methyl-maleic acid and acid anhydrides and mono alkyl ester thereof, and there is the Vinyl Ether of carboxyl, for example propyloic Vinyl Ether and carboxylic propyl vinyl ether.The example of sulfonic acid monomer comprises styrene sulfonic acid, 2-acrylamide-2-methyl propane sulfonic, 3-sulfopropyl (methyl) acrylate, two-(3-sulfopropyl)-itaconic ester and salt thereof.Other examples comprise the acrylic acid sulfuric acid monoester of 2-hydroxyethyl (methyl) and salt thereof.The example of phosphorus acid monomer comprises vinyl phosphonate, vinyl phosphate, acid phosphine oxygen base ethyl (methyl) acrylate, acid phosphine oxygen base propyl group (methyl) acrylate, two (methacryloxyethyl) phosphoric acid ester, phenylbenzene-2-methacryloxyethyl phosphoric acid ester, phenylbenzene-2-acryloxy ethyl phosphonic acid ester, dibutyl-2-methacryloxyethyl phosphoric acid ester, dibutyl-2-acryloxy ethyl phosphonic acid ester and dioctyl-2-(methyl) acryloxy ethyl phosphonic acid ester.Anionic monomer is desirably the monomer with (methyl) vinylformic acid or sulfonic acid, more desirably for being the monomer of the ammonium salts producing before and after polymerization.For example, by reacting to form ammonium salt with tertiary amine or quaternary ammonium hydroxide.

Having the fluorine-based monomer that serves as charged group is for example to have fluorine-based (methyl) acrylate monomer.Specific examples comprises (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid five fluorine propyl ester, (methyl) vinylformic acid perfluor ethyl ester, (methyl) vinylformic acid perfluoro butyl ethyl ester, (methyl) vinylformic acid perfluoro capryl ethyl ester, (methyl) vinylformic acid perfluor decyl ethyl ester, (methyl) vinylformic acid trifluoromethyl trifluoro ethyl ester and (methyl) vinylformic acid hexafluoro butyl ester.

Other monomers can be nonionic monomers, for example (methyl) vinyl cyanide, (methyl) alkyl acrylate, (methyl) acrylamide, ethene, propylene, divinyl, isoprene, iso-butylene, (methyl) acrylamide, vinylbenzene, vinylcarbazole, vinylbenzene, styrene derivatives, polyethyleneglycol (methyl) acrylate, vinylchlorid, vinylidene chloride, isoprene, divinyl, vinyl pyrrolidone, (methyl) Hydroxyethyl Acrylate and (methyl) vinylformic acid hydroxyl butyl ester that through N-dialkyl group, replace.

Having the monomer of charged group and the copolymerization ratio of other monomers changes according to the desirable quantity of electric charge on particle.There is the monomer of charged group and the copolymerization ratio of other monomers is selected typically from the molar ratio range of 1: 100 to 100: 0.

The weight average molecular weight of the second polymkeric substance is desirably 1,000 to 1,000,000, is more desirably 10,000 to 200,000.

When the first polymkeric substance has acidic-group as A ¹time, the charged group of the second polymkeric substance is preferably basic group.When the first polymkeric substance has basic group as A ¹time, the charged group of the second polymkeric substance is preferably acidic-group.

Below describe the electronegative particle with alkali in detail as the embodiment of the particle containing tinting material of the present invention.The polymkeric substance (the second polymkeric substance) that these electronegative particles can have alkali by use is manufactured.But, because alkali do not serve as can electronegative charged group, so the second polymkeric substance preferably has the independent group that can serve as charged group.That the example of charged group comprises is fluorine-based, carboxyl, formate, sulfonic group, sulfonate radical, phosphate and phosphate radical.Charged group is desirably fluorine-based.

That is the electronegative particle that, has alkali is preferably used has alkali and fluorine-based the second polymkeric substance as charged group.The example with alkali and fluorine-based these polymkeric substance comprises containing alkali monomer, has the multipolymer of fluorine-based monomer and (while needing) other monomers (nonionic monomers).Described monomer can be the monomer identical with the monomer that is used to form polymkeric substance above.

Except the Component units derived from described monomer, the second polymkeric substance can also have the Component units being configured by silicone monomer.Silicone monomer can be silicone macromonomer.

The example of silicone monomer or macromonomer is included in an end and has (methyl) acrylate-based dimethyl-silicon one monomers (for example, available from Silaplane FM-0711, FM-0721 and the FM-072 (trade(brand)name) 5 of Chisso Corporation; With X-22-174DX, X-22-2426 and the X-22-2475 (trade(brand)name) available from silicone company of SHIN-ETSU HANTOTAI).Derive the Component units P of the first polymkeric substance ¹silicone macromonomer represent another example.

Except the first polymkeric substance and the second polymkeric substance, containing the particle of tinting material, can also contain the silicone polymer of adhesion (for example, by bond or coating) to particle surface.Described silicone polymer is the polymer compound for example with silicone chains, more particularly and preferably, has the compound of silicone chains (silicone graft chain) as the side chain of the main chain of main polymer compound.The weight average molecular weight of described silicone polymer is desirably 500 to 1,000,000, is more desirably 1,000 to 1,000,000.Except the Component units derived from described silicone monomer or macromonomer, described silicone polymer can also have the Component units derived from non-silicone monomer.

(4) other components

Particle containing tinting material of the present invention can comprise the material except the first polymkeric substance, tinting material and the second polymkeric substance of optionally adding in addition.The example of these additional materials comprises charge control material and magneticsubstance.Charge control material can be the known charge control material for electrophotographic toner material, comprise the ammonium salt of for example entrusting, for example cetyl pyridinium base muriate, BONTRON P-51, BONTRON P-53, BONTRON E-84, BONTRON E-81 (trade(brand)name, available from east chemistry (the Orient Chemical Industries. of Industrial Co., Ltd, Co., Ltd.)), salicylic acid metal complex, phenol condensation products, tetraphenyl compound, metal oxide particle and the metal oxide particle surface through various coupler processing.

Magneticsubstance can be the inorganic or organo-metallic material of optionally crossing through pigment application.Transparent Magnetic Materials, particularly transparent organo-metallic material is better, because these materials are not easy to suppress the colour developing of coloured pigment, and has the proportion less than inorganic magnetic material.The example of colored magneticsubstance (colorized coated material) comprises the colored magnetic powder of minor diameter described in Japanese Patent Laid-Open 2003-131420 communique.Colored magneticsubstance can comprise core magnetic particle and be laminated to the lip-deep color layer of magnetic particle.For instance, described color layer can be to utilize pigment etc. to make magnetic particle have the color layer of opaque color.But, for instance, preferably use optical interference film.Optical interference film is colourless material (for example SiO with the thickness identical with optical wavelength ₂and TiO ₂) film, and by the optical interference with in described film, optionally reflect the light with certain wavelength.

(5) containing the particle manufacturing process of tinting material

Technique for the manufacture of the particle containing tinting material of the present invention is not particularly limited.A kind of exemplary processes is below described.This exemplary processes is the embodiment that contains the first polymkeric substance and the second polymkeric substance.Utilize this technique, can be manufactured on centre portions contain tinting material, the second polymkeric substance around described tinting material and the first Polymer adsorption the particle containing tinting material on outside.

Described technique comprises following steps: stir and emulsification contains described the second polymkeric substance, described tinting material, the first solvent (can form the poor solvent of external phase) and for dissolving described the second polymkeric substance, incompatible with described the first solvent and have the mixing solutions of more lower boiling the second solvent (can form the good solvent of disperse phase) with described the first solvent phase ratio; From the mixing solutions of emulsification, remove described the second solvent to form the painted particle (particle) of process that contains described the second polymkeric substance and described tinting material; And mix described the first polymkeric substance.This technique has represented a kind of technology that is called desiccating method in liquid.Described technique can comprise subsequent step in addition, for example, wash particle (removal ionic impurity), replace dispersion medium, concentrate dispersion medium and dilution dispersion medium.

Utilize this technology, can obtain the particle containing tinting material of the present invention at the dispersion liquid as in the first solvent of dispersion medium.Described the first solvent can be for as after a while for example, by the dispersion medium of the dispersion liquid of the present invention of being described (silicone oil and paraffinic hydrocarbon solvent).Described dispersion liquid can be directly used in various application, for example display mediums.

Particle manufacturing process containing tinting material of the present invention is not limited to above-mentioned manufacturing process, and can use additive method, for example, pulverize, cohesion, dispersion polymerization and suspension polymerization.Utilize particle or the particle dispersion of these method manufactures can be directly used in various application, for example display mediums, or can after for example washing particle (removal ionic impurity), replace dispersion medium, evaporate dispersion medium and diluting other techniques such as dispersion medium, use.

(6) containing the character of the particle of tinting material

The size of the particle containing tinting material of the present invention is not particularly limited, and can set preferable range according to intended purpose.When using particle as display mediums, median size is preferably 0.05 to 10 micron, more preferably 0.1 to 1 micron.Median size can utilize known method to measure, for example, relate to the method for measuring with transmission electron microscope and utilize the automatic particle size distribution measurement device of commercially available ultracentrifugation and the measurement of light diffusing particles particle size distribution measurement device to have the method for the dispersible pigment dispersion of proper concn.

In an embodiment of the particle containing tinting material of the present invention, the described particle containing tinting material is the electrophoresis particle with electrophoresis.The particle of this embodiment preferably contains described the second polymkeric substance.The particle of this embodiment can be for adopting the multiple technologies field of principle of electrophoresis.An example is the indicating meter particle for electrophoretic electronic paper.

2. contain the particle dispersion of tinting material

The present invention is about the particle dispersion containing tinting material that contains the particle containing tinting material of the present invention and dispersion medium.

The preferred concentration range containing the particle of tinting material in described dispersion liquid changes according to purposes, and from the viewpoint of dispersity and dispersion stabilization, is preferably less than or equal to 30 quality %, and more preferably 0.1 quality % is to 30 quality %.In these concentration ranges, can in display mediums application, obtain desirable indicating characteristic and response feature.In an embodiment who contains the multiple particle containing tinting material, containing the total amount of the particle of tinting material preferably in above-mentioned scope.

According to the particle concentration in the particle dispersion of the present embodiment, be to select according to indicating characteristic, response feature and purposes, and be to select within the scope of 30 quality % from 0.1 quality % ideally.When mixing the particle of different colours, the total amount of described particle is ideally within the scope of this.

Dispersion liquid of the present invention can contain more than a kind of particle containing tinting material.For instance, can contain different particle aspect the strength of electric field that starts to move at for example tone, charge polarity and particle under electric field action.The dispersion liquid of this embodiment is suitable as color monitor medium.The combination of two or more particles can be the combination with the particle of the different charge polarities of different color harmonies, or the combination of different particles aspect the strength of electric field that starts to move under electric field action at color harmony particle.

Dispersion medium

Dispersion medium is not particularly limited, and can suitably select and use one or more solvents according to intended purpose.The example of dispersion medium comprises the high boiling solvent that silicone oil, paraffinic hydrocarbon solvent, fluorine liquid and petroleum derivation go out.Particularly preferably be silicone oil and paraffinic hydrocarbon solvent.More preferably silicone oil.Dispersion medium is also preferably the mixed solvent of silicone oil and the solvent except silicone oil.

The specific examples of silicone oil comprises the silicone oil (for example dimethylsilicone oil, diethyl silicone oil, methylethyl silicone oil, methyl phenyl silicone oil and phenylbenzene silicone oil) that alkyl is connected to siloxane bond.Dimethyl silscone is desirable especially.

Other additives

Dispersion liquid of the present invention can contain additive when needed, for example acid, alkali, salt, dispersion agent, dispersion stabilizer, for anti-oxidation or absorb ultraviolet stablizer, biocide and sanitas.In addition, can in particle dispersion of the present invention, add charge control agent.

In dispersion liquid of the present invention, containing the first polymkeric substance contained in the particle of tinting material can be from described particle partial solution from, and may reside in dispersion medium.

Particle dispersion of the present invention has widespread use, and is suitable for adopting the technical field of principle of electrophoresis, comprises electrophoretic display device (EPD) medium, the photochromic medium of electrophoresis (photochromic element) and liquid development electrophotographic system liquid toner.The photochromic medium of electrophoretic display device (EPD) medium and electrophoresis (photochromic element) can belong to wherein one group of particle in the relative direction of electrode (substrate) or at the known system of move upward along the side of electrode (substrate) plane (they are called element in plane), can be maybe the hybrid element of these systems.

In an embodiment of the particle dispersion containing tinting material of the present invention, containing the particle dispersion of tinting material, contain one or more electrophoresis particles moving as depending on electric field containing the particle of tinting material of the present invention, and the dispersion medium configuring with silicone oil.In the present embodiment, described the first polymkeric substance is preferably adsorbed onto the surface containing the particle of tinting material.

Typically, particle may be applied to the cohesive force between particle in time and assemble in the case of existing via polymeric dispersant, and the reversible aggregation of particle and redispersion feature may be carried out and fluctuation along with gathering.This may cause electric field reaction (threshold value feature) to change and produce inhomogeneous indicating meter.According in the particle dispersion of the present embodiment, by using concrete formula (1) first polymkeric substance to offset this situation as the polymeric dispersant of controlling the cohesive force between particle.Even because believe that described the first polymkeric substance also can suppress the progress of time-dependent manner particle accumulation after the reversible particle accumulation repeating and redispersion, so can suppress the fluctuation of reversible particle accumulation and redispersion feature.Because the particle dispersion of the present embodiment may suppress the progress of the time-dependent manner particle accumulation in display mediums or display equipment application, so can realize stable circulation indicating meter.

According to the particle dispersion of the present embodiment preferably through being configured to make the functional group of described tinting material or interacting and functional group's interaction of described the first polymkeric substance by acid-alkali around the functional group of described second polymkeric substance (if present) of described tinting material.

Specifically, described particle dispersion preferably through configuration so that:

1) will there is the tinting material of alkali or use with first combination of polymers with acid around second polymkeric substance with alkali of described tinting material; Or

2) will there is sour tinting material or use with first combination of polymers with alkali around second polymkeric substance with acid of described tinting material.

Utilize these configurations, according to the particle dispersion of the present embodiment, suppress to depend in electrophoretic display device (EPD) media applications for example the charge polarity fluctuation of the particle that electric field moves.Exactly, when thering is the tinting material of alkali or can stablize described particle with negative charge when second polymkeric substance with alkali of described tinting material be used with first combination of polymers with acid.

In display mediums or display equipment application, according to the particle dispersion of the present embodiment, suppress the charge polarity fluctuation of indicating meter particle.Specifically, because have in the particle (particle group) of identical polar, there is the less particle with opposite polarity, so can suppress the blend of colors in indicating meter.

3. polymer compound

The present invention also has about the polymer compound by representing with following formula (1 ').

(A ¹-R ⁴-S) _n-R ¹-(R ³-P ¹) _m (1′)

In described formula, R ¹represent the organic linking group of (m+n) valency; R ⁴represent separately singly-bound or divalent linker; S represents sulphur atom; A ¹represent separately the unit price organic group that contains at least one group of selecting from following group: organic dye residue, heterocycle residue, acidic-group, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, the alkyl with more than 4 carbon atom, alkoxysilane group, epoxy group(ing), isocyanate group and hydroxyl; A ¹and R ²independently of one another can be identical or different in the situation that thering is subscript n; M representative digit 1 to 8, and n representative digit 2 to 9, wherein m+n meets 3 to 10; R ³represent separately singly-bound or divalent linker; P ¹represent to contain Si bond owner chain, and can comprise multiple Component units, R ³and P ¹independently of one another can be identical or different in the situation that thering is subscript m;

-(P ²) _x-(P ³) _y-(P ⁴) _z (2)，

Group in described formula has and identical definition mentioned above and preferable range.

For instance, the weight average molecular weight of polymer compound of the present invention is desirably 10,000 to 1,000,000, is more desirably 50,000 to 300,000.Weight average molecular weight can be passed through gel permeation chromatography (Gel Permeation Chromatography, GPC) and measure.

Polymer compound of the present invention can be by synthesizing to Lung biopsy by above-mentioned first method, and preferably by synthesizing with Lung biopsy.

Polymer compound of the present invention can be used for multiple application, comprises dispersion agent and charge adjusting agent.

Example

Following use-case is described the present invention in more detail.Material, reagent, amount, ratio, program and other conditions in following instance, used can suitably change, and its restricted condition does not deviate from purport of the present invention for these change.Therefore, scope of the present invention should be interpreted as in the boundary of specific examples described below by narrow.

Hereinafter, unless statement in addition, " part " and " % " is respectively " mass parts " and " quality % ".

1. synthetic example

(1) synthetic example C-1 is to C-31

By synthesizing the polymer compound C-1 being represented by formula (1) with following methods to C-31 (the first polymkeric substance).

The synthetic mercaptan compound being represented by formula (5)

First, by synthesizing chain-transfer agent B-1 with following methods to B-7 (mercaptan compound being represented by formula (5)).

[synthetic example B-1]

By diisoamyl tetrol six (3-mercaptopropionic acid ester) [DPMP; (the Sakai Chemical Industry Co. of Sakai chemical industry company limited, Ltd.)] (7.83 parts) are dissolved in dimethyl formamide (93.60 parts) with the compound (A-1) (15.57 parts) with following absorbed portion and carbon-to-carbon double bond, and mixture are heated to 70 ℃ under nitrogen gas stream.Add 2, two (2,4-methyl pentane nitrile) [V-65 (trade(brand)name), and (the Wako Pure Chemical Industries of Guang Chunyao chemical industry company limited of 2 '-azo, Ltd.)] (0.06 part) afterwards, heats mixture 3 hours.Add extra V-65 (trade(brand)name) (0.06 part) afterwards, allow under nitrogen gas stream, to react 3 hours at 70 ℃.20% solution of mercaptan compound (chain-transfer agent B-1) below obtaining after mixture cool to room temperature.

[Chemical formula 2 4]

[synthetic example B-2]

With obtaining 20% solution of following mercaptan compound (chain-transfer agent B-2) with mode identical in synthetic example B-1, but the compound with absorbed portion and carbon-to-carbon double bond (A-1) (15.57 parts) using in synthetic example B-1 and dimethyl formamide (93.60 parts) are there is respectively instead to compound (A-2) (4.47 parts) and the dimethyl formamide (78.38 parts) of absorbed portion and carbon-to-carbon double bond.

[Chemical formula 2 5]

[synthetic example B-3]

With obtaining 20% solution of following mercaptan compound (chain-transfer agent B-3) with mode identical in synthetic example B-1, but the compound with absorbed portion and carbon-to-carbon double bond (A-1) (15.57 parts) using in synthetic example B-1 and dimethyl formamide (93.60 parts) are there is respectively instead to compound (A-3) (6.18 parts) and the dimethyl formamide (89.78 parts) of absorbed portion and carbon-to-carbon double bond.

[Chemical formula 2 6]

[synthetic example B-4]

With obtaining 20% solution of following mercaptan compound (chain-transfer agent B-4) with mode identical in synthetic example B-1, but the compound with absorbed portion and carbon-to-carbon double bond (A-1) (15.57 parts) using in synthetic example B-1 and dimethyl formamide (93.60 parts) are there is respectively instead to compound (A-4) (9.99 parts) and the dimethyl formamide (101.4 parts) of absorbed portion and carbon-to-carbon double bond.

[Chemical formula 2 7]

[synthetic example B-5]

With obtaining 20% solution of following mercaptan compound (chain-transfer agent B-5) with mode identical in synthetic example B-1, but the compound with absorbed portion and carbon-to-carbon double bond (A-1) (15.57 parts) using in synthetic example B-1 and dimethyl formamide (93.60 parts) are there is respectively instead to compound (A-5) (6.8 parts) and the dimethyl formamide (89.99 parts) of absorbed portion and carbon-to-carbon double bond.

[Chemical formula 2 8]

[synthetic example B-6]

With obtaining 30% solution of following mercaptan compound (chain-transfer agent B-6) with mode identical in synthetic example B-1, but the compound with absorbed portion and carbon-to-carbon double bond (A-1) (15.57 parts) using in synthetic example B-1 and dimethyl formamide (93.60 parts) are there is respectively instead to compound (A-6) (12.61 parts) and the dimethyl formamide (40.82 parts) of absorbed portion and carbon-to-carbon double bond.

[Chemical formula 2 9]

[synthetic example B-7]

With obtaining 30% solution of following mercaptan compound (chain-transfer agent B-7) with mode identical in synthetic example B-1, but the compound with absorbed portion and carbon-to-carbon double bond (A-1) (15.57 parts) using in synthetic example B-1 and dimethyl formamide (93.60 parts) are there is respectively instead to compound (A-7) (14.7 parts) and the dimethyl formamide (41.75 parts) of absorbed portion and carbon-to-carbon double bond.

[chemical formula 30]

The synthetic polymer compound C-1 being represented by formula (1) is to C-31 (the first polymkeric substance)

By coming synthetic polymer Compound C-1 with following methods to C-31 (the first polymkeric substance).

[synthetic example C-1]

Under nitrogen gas stream, by the 20% chain-transfer agent B-1 solution (46.80 parts) obtaining in synthetic example B-1, FM-0711, (trade(brand)name, containing Si monomer; 14 _-65 parts), methyl methacrylate (MMA; Monomer; 2.20 parts) and methacrylic acid (MAA; Monomer; 3.15 parts) mixing solutions be heated to 80 ℃.Add 2, two (the isopropyl cyanide) [AIBN of 2 '-azo, with Guang Chunyao chemical industry company limited] (0.005 part) afterwards by mixture heating 3 hours, and by adding again AIBN (0.005 part) to allow to react under nitrogen gas stream 3 hours at 80 ℃.By mixture cool to room temperature, and use acetone diluted.After a large amount of methyl alcohol redeposition, vacuum-drying product, to obtain the solid (C-1: with regard to polystyrene, weight average molecular weight is 32,000 of following polymer compound; The first polymkeric substance; 19 parts).

[chemical formula 31]

[synthetic example C-2]

With obtaining the solid (C-2: with regard to polystyrene, weight average molecular weight is 15,000 of following polymer compound with mode identical in synthetic example C-1; The first 19 parts, polymkeric substance), but with the AIBN of 0.005 part of use, be with 0.010 part of use in synthetic example C-1.

[chemical formula 32]

[synthetic example C-3]

With obtaining the solid (C-3: with regard to polystyrene, weight average molecular weight is 6,000 of following polymer compound with mode identical in synthetic example C-1; The first polymkeric substance; 19 parts), but with the AIBN of 0.005 part of use, be with 0.020 part of use in synthetic example C-1.

[chemical formula 33]

[synthetic example C-4 is to C-31]

With manufacturing polymer compound C-4 to C-31 (the first polymkeric substance) with mode identical in synthetic example C-1, but change as Table 1 and Table 2 below the type of chain-transfer agent kind, monomer and amount, AIBN amount and redeposition method.

[table 1]

The structure of the polymer compound of above synthesized is below provided.Symbol (for example C-4) is corresponding to the synthetic example number of using in table 1.

[chemical formula 34]

[chemical formula 35]

[chemical formula 36]

[chemical formula 37]

[chemical formula 38]

2. preparation contains the particle of tinting material and the particle dispersion containing tinting material

1) example A

(example A-1)

Preparation cyan particles (particle of positively charged) and particle dispersion

(manufacture has the second amino polymkeric substance)

First, by N-V-Pyrol RC (85 mass parts), Silaplane FM-0721 (trade(brand)name, silicone chains monomer; 10 mass parts) and diethyl aminoethyl methacrylate (there is the monomer of charged group; 5 mass parts) mix with Virahol (100 mass parts).Dissolve AIBN (polymerization initiator; 0.2 mass parts) afterwards, polymerization 6 hours under nitrogen at 70 ℃.With cyclohexane give, be that redeposition solvent carrys out purified product and dry, to obtain polymkeric substance.

Described polymkeric substance dissolves in distilled water, even and be also soluble under 30 quality % concentration, and do not form any throw out.These results show that described polymkeric substance is water-soluble polymers.

(preparation is containing particle and the particle dispersion of tinting material)

By the 10 quality % aqueous solution (3 mass parts) of described polymkeric substance and pigment solution (the soft Li Bise (Unisperse) (trade(brand)name) of 1 mass parts through water-dispersion; Cyan; Vapour Bagong department (Ciba); Pigment concentration 26 quality %) mix, to prepare the aqueous solution of described polymkeric substance and described pigment.Thereafter, will be through silicone modified acryl polymkeric substance KP545 (trade(brand)name, emulsifying agent; Chemical Co., Ltd. of SHIN-ETSU HANTOTAI) join dimethylsilicone oil (KF-96-2CS (trade(brand)name); Silicone company of SHIN-ETSU HANTOTAI) in, to prepare the 3 quality % silicone solutions of KP545 (trade(brand)name).After the described aqueous solution is mixed with the 3 quality % silicone solutions (10 mass parts) of KP545 (trade(brand)name), disperse described material containing the aqueous solution of polymkeric substance and pigment, to be scattered in the suspension (viscosity 2 centistokes) in silicone oil with preparation by ultrasonic homogenizer.

At the lower heating of decompression (2 kPas) (70 ℃) described suspension, to remove moisture, and obtain and contain the particle dispersion of the particle containing polymkeric substance and pigment in silicone oil.Monobromethane (0.1 mass parts) is joined in described particle dispersion, and at 80 ℃, described dispersion liquid is heated 2 hours, to the amino of the monomer component diethyl aminoethyl methacrylate of polymkeric substance is changed into season amino.Then under reduced pressure remove unreacted monobromethane.The solids content of gained particle dispersion is 8.2 quality %, as utilizes the quality measured values before and after dry silicone oil to calculate.The volume average particle size of the particle in dispersion liquid is 260 nanometers, as used laser light scattering and diffraction grain-size measuring apparatus (Horiba LA-300 (trade(brand)name)) measured.

The polymer compound C-1 (0.5 mass parts) obtaining is above joined in 100 mass parts cyan particles dispersion liquid A (solids content 1.5%), to obtain particle and the particle dispersion containing tinting material.

After charge polarity assessment, the polarity of finding the cyan particles group in described dispersion liquid is for just, described dispersion liquid is sealed in to electrophoresis between paired electrode substrate and under applied direct current (DC) voltage in described assessment, to check direction of motion.

(example A-2 is to A-31 and comparative example A-1 to A-4)

With preparing particle dispersion with mode identical in example A1, but as shown in following table, change polymer compound kind (the first polymkeric substance) and polymer compound concentration.

[the polymeric dispersant C-32 of synthetic comparative example]

By Silaplane FM0711 (trade(brand)name, Chisso Corporation; 4.5 mass parts), methacrylic acid is (with Guang Chunyao chemical industry company limited; 0.5 mass parts), Virahol (solvent; 10 mass parts), V-65 (trade(brand)name, the two methyl pentane nitriles of azo; With Guang Chunyao chemical industry company limited; Polymerization initiator; 0.02 mass parts) mix, and at 55 ℃, react 24 hours after abundant nitrogen replacement.After polymerization, drying under reduced pressure product to be to remove solvent and unreacted monomer, and after purifying, obtains comparative polymers dispersing agent C-32.Productive rate is 98%.GPC molecular weight measurement shows that, with regard to polystyrene standards, weight average molecular weight is 120,000.

[the polymeric dispersant C-33 of synthetic comparative example]

Under nitrogen gas stream, 20% solution (46.80 parts) and the methyl methacrylate (MMA of the chain-transfer agent B-1 obtaining in example B-1 will be synthesized; Monomer; 20 parts) be heated to 80 ℃.Add two (isopropyl cyanide) [AIBN, and Guang Chunyao chemical industry company limited of 2,2 '-azo; 0.013 part] afterwards by mixture heating 3 hours, and by adding again AIBN (0.013 part) to allow to react again under nitrogen gas stream 3 hours at 80 ℃.By mixture cool to room temperature, by acetone diluted, and with a large amount of methyl alcohol redeposition.Then vacuum-drying product, to obtain the solid (C-33: with regard to polystyrene, weight average molecular weight is 14,000 of polymeric dispersant of comparative example; 19 parts).

[the polymeric dispersant C-34 of synthetic comparative example]

Under nitrogen gas stream, 20% solution (46.80 parts) and the methyl methacrylate (MMA of the chain-transfer agent B-1 obtaining in example B-3 will be synthesized; Monomer; 20 parts) be heated to 80 ℃.Add two (isopropyl cyanide) [AIBN, and Guang Chunyao chemical industry company limited of 2,2 '-azo; 0.013 part] afterwards by mixture heating 3 hours, and by adding again AIBN (0.013 part) to allow to react again under nitrogen gas stream 3 hours at 80 ℃.By mixture cool to room temperature, by acetone diluted, and with a large amount of methyl alcohol redeposition.Then vacuum-drying product, to obtain the solid (C-44: with regard to polystyrene, weight average molecular weight is 14,000 of polymeric dispersant of comparative example; 19 parts).

[assessment]

Assess each particle dispersion by mode described below.

(viscosity measurement and assessment)

Use E type viscometer (trade(brand)name) to measure after the dispersion of each particle dispersion viscosities il at once ¹with the viscosities il of disperseing latter a week ²(under room temperature).Then assess thickening degree.During assessment result is provided in the following table.Viscosity is lower, means that dispersity and dispersion stabilization are unreasonable to think.

[table 2]

(2) example B

(example B-1)

Preparation red-purple particle B (have the particle of acidic group: electronegative particle) and particle dispersion

(manufacture has the second polymkeric substance of carboxyl)

First, by vinylformic acid 2-hydroxy methacrylate (85 mass parts), Silaplane FM-0721 (trade(brand)name, silicone chains monomer; 10 mass parts) and methacrylic acid (there is the monomer of charged group; 5 mass parts) mix with Virahol (100 mass parts).Dissolve AIBN (2,2 '-azo two (isopropyl cyanide); Polymerization initiator; 0.2 mass parts) afterwards, polymerization 6 hours under nitrogen at 70 ℃.With cyclohexane give, be that redeposition solvent carrys out purified product and dry, to obtain polymkeric substance.

By the 10 quality % aqueous solution (3 mass parts) of described polymkeric substance and pigment solution (the soft Li Bise (Unisperse) (trade(brand)name) of 1 mass parts through water-dispersion; Red-purple; Vapour Bagong department; Pigment concentration 16 quality %) mix, to prepare the aqueous solution of described polymkeric substance and described pigment.Thereafter, will be through silicone modified acryl polymkeric substance KP545 (trade(brand)name, emulsifying agent; Chemical Co., Ltd. of SHIN-ETSU HANTOTAI) join dimethylsilicone oil (KF-96-2CS (trade(brand)name); Silicone company of SHIN-ETSU HANTOTAI) in, to prepare the 3 quality % silicone solutions of KP545 (trade(brand)name).After the described aqueous solution is mixed with the 3 quality % silicone solutions (10 mass parts) of KP545 (trade(brand)name), disperse described material containing the aqueous solution of polymkeric substance and pigment, to be scattered in the suspension (viscosity 2 centistokes) in silicone oil with preparation by ultrasonic homogenizer.

The lower heating of decompression (2 kPas) (70 ℃) described suspension 2 hours, to remove moisture, and obtain and contain the particle dispersion of the particle containing polymkeric substance and pigment in silicone oil.Then by chemical equimolar amount three amine join in described particle dispersion to form methacrylic acid and the salt monomer component as described polymkeric substance.

The solids content of gained particle dispersion is 7.2 quality %, as utilizes the quality measured values before and after dry silicone oil to calculate.The volume average particle size of the electrophoresis particle in dispersion liquid is 280 nanometers, as used laser light scattering and diffraction grain-size measuring apparatus (Horiba LA-300 (trade(brand)name)) measured.

The polymeric dispersant C-1 (0.5 mass parts) obtaining is above joined in 100 mass parts red-purple particle dispersion B (solids content 1.5%), to obtain particle dispersion.

After charge polarity assessment, find that the polarity of the red-purple particle group in described dispersion liquid is for negative, described dispersion liquid is sealed in to electrophoresis between paired electrode substrate and under applied direct current (DC) voltage in described assessment, to check direction of motion.

(example B-2 is to B-31 and comparative example B-1 to B-4)

With preparing particle dispersion with mode identical in example B1, but as shown in following table, change polymer compound kind (the first polymkeric substance) and polymer compound concentration.

[assessment]

Assess particle dispersion by mode described below.

(viscosity measurement and assessment)

Use E type viscometer to measure described particle dispersion viscosities il at once after dispersion ¹with the viscosities il of disperseing latter a week ²(under room temperature).Then assess thickening degree.During assessment result is provided in the following table.Viscosity is lower, means that dispersity and dispersion stabilization are unreasonable to think.

[table 3]

Claims

1. containing the particle of tinting material, it comprises tinting material and by the first polymkeric substance representing with following formula (1):

(A ¹-R ²) _n-R ¹-(R ³-p ¹) _m (1)，

2. the particle containing tinting material according to claim 1, also comprises second polymkeric substance with charged group.

3. the particle containing tinting material according to claim 1 and 2, the A in wherein said formula (1) ¹be acidic-group, and the charged group of described the second polymkeric substance is basic group.

4. the particle containing tinting material according to claim 1 and 2, the A in wherein said formula (1) ¹be basic group, and the charged group of described the second polymkeric substance is acidic-group.

According to described in any one in claim 1 to 4 containing the particle of tinting material, it is the Component units of 1,000 to 10,000 silicone macromonomer that wherein said the first polymkeric substance has derived from weight average molecular weight.

6. according to the particle containing tinting material described in any one in claim 1 to 5, the P in wherein said formula (1) ¹by the main polymer chain representing with following formula (2):

-(P ²) _x-(P ³) _y-(P ⁴) _z (2)，

According to described in any one in claim 1 to 6 containing the particle of tinting material, wherein in described formula (2), x is 10 to 30, y to be 10 to 30, and z is 40 to 80.

8. according to the particle containing tinting material described in any one in claim 1 to 7, the wherein said particle containing tinting material is electrophoresis particle.

9. containing a particle dispersion for tinting material, comprise according to particle and dispersion medium containing tinting material described in any one in claim 1 to 8.

10. the particle dispersion containing tinting material according to claim 9, wherein said dispersion medium contains at least one that select from silicone oil and paraffinic hydrocarbon.

11. 1 kinds of polymer compounds, by representing with following formula (1 '):

(A ¹-R ⁴-S) _n-R ¹-(R ³-p ¹) _m (1′)，

-(P ²) _x-(P ³) _y-(P ⁴) _z (2)，